CN109912234B - Glass fiber coating and preparation method thereof - Google Patents
Glass fiber coating and preparation method thereof Download PDFInfo
- Publication number
- CN109912234B CN109912234B CN201910153795.2A CN201910153795A CN109912234B CN 109912234 B CN109912234 B CN 109912234B CN 201910153795 A CN201910153795 A CN 201910153795A CN 109912234 B CN109912234 B CN 109912234B
- Authority
- CN
- China
- Prior art keywords
- parts
- cationic
- urea
- emulsion
- acrylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Paints Or Removers (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention discloses a high-performance glass fiber coating and a preparation method thereof, and the glass fiber coating and the preparation method thereof aim to solve the technical problems of poor alkali resistance and poor storage stability of the conventional urea resin coating; the glass fiber coating comprises the following raw materials in parts by weight: 40-70 parts of water, 20-30 parts of acrylate monomers, 1-5 parts of acrylate functional monomers, 10-30 parts of modified urea-formaldehyde resin glue, 0.5-5 parts of polymeric stabilizer, 0.1-1.5 parts of azo-bis-isobutyramidine hydrochloride, 0.1-0.5 part of azo-bis-isobutyronitrile, 0.1-3 parts of cationic emulsifier or cationic reaction type emulsifier, 4-7 parts of cationic starch dispersion, 0.05-0.5 part of acid-base buffer and 0.1-5 parts of chain transfer additive. By adopting the technical scheme, the water resistance, alkali resistance and storage stability of the coating can be effectively improved, and the coating has the performance advantages of urea-formaldehyde resin and acrylate resin and simultaneously improves the overall performance of the polymer.
Description
Technical Field
The invention belongs to the fields of coating, painting and coating, and particularly relates to a high-performance glass fiber coating and a preparation method thereof.
Background
Cationic Polymer Emulsion (CPE) is homopolymer or copolymer emulsion prepared by Cationic emulsifier or monomer with positive charge, and is basically characterized in that the surface of emulsion particles or the polymer has positive charge; the cationic polymer emulsion has good balance performance on positive and negative charges, and also has the functions of sterilization, flocculation, slow release and the like, so the cationic polymer emulsion has the functions incomparable with anionic or nonionic emulsions in many aspects.
Acrylic polymer emulsions have been the focus of research because they have excellent film properties, water resistance, adhesion and coating elasticity; the acrylic cationic polymer emulsion has attracted attention because of the positive charge, which endows the acrylic polymer with better antibacterial property, and can improve the stability, mechanical property and the like of the emulsion. Based on the antibacterial and anticorrosive properties of the cationic polymer emulsion, the cationic property such as high binding fastness with anionic substances and excellent film-forming properties, the cationic polymer emulsion can be applied to the fields of coating, adhesives and the like, so that a coating material with antibacterial and anticorrosive properties is obtained. In particular to the field of glass fiber mesh cloth coating, in the glass fiber coating process, conditions favorable for growth of mildew and rot bacteria, such as long latex exposure time, more auxiliary additives, high working environment temperature and the like, often exist, and the cationic coating emulsion can well ensure the antibacterial and mildew-proof performance of the latex.
Interpenetrating Polymer Network (IPN) is an interwoven Network Polymer formed by mutually penetrating two or more than two crosslinked polymers; the composite material is a new field of polymer blending modification technology development, and has the advantages of both physical blending and chemical copolymerization, so that the composite material has many valuable properties.
According to different synthesis methods, the IPNs can be divided into different types, which can be classified into synchronous IPNs (sin), stepwise IPNs (sipns), interpenetrating network elastomers (IENs), and latex IPNs (lipns); LIPN is an emerging IPN composite material, LIPN generally refers to a broad latex interpenetrating polymer network, and from a composition perspective, such an interpenetrating polymer can be further divided into two types, i.e., LIPN, which means that both polymers forming the interpenetrating network are crosslinked, and latex semi-IPN, which means that only one of the two polymers is crosslinked while the other is linear, depending on whether the polymers are crosslinked or not. The IPN technology carries out molecular-level or supermolecular-level physical blending of various polymers in a chemical method, takes advantages of both physical blending and chemical copolymerization by using forced compatibility and synergistic effect, and endows a polymer material with a plurality of valuable properties. LIPN is one of the most active fields in IPN technology, not only can be directly used as a coating base material, but also is beneficial to the later processing and forming of plastics. In the field of glass fiber coating, a polymer coating film is required to have very good alkali resistance and water resistance, and the swelling or degradation of the coating film is prevented, otherwise, the strength of the glass fiber in the coating layer is obviously reduced when the glass fiber is exposed in an alkali liquor environment, and the IPN structural polymer can obviously improve the water resistance and alkali resistance of the coating layer, so that the IPN structural polymer can be utilized.
Urea-formaldehyde resin (UF resin), which is an insoluble, infusible thermosetting resin formed by polycondensation of urea and formaldehyde in the presence of a catalyst (alkaline or acidic catalyst) to form an initial urea-formaldehyde resin and then in the presence of a curing agent or an auxiliary agent. The cured urea-formaldehyde resin is lighter than phenol-formaldehyde resin, translucent, weak acid and weak base resistant, good in insulating property, excellent in wear resistance and low in price, is the variety with the largest dosage in the adhesive, and particularly in the manufacture of various artificial boards in the wood processing industry, the urea-formaldehyde resin and the modified products thereof account for about 90% of the total dosage of the adhesive.
Zhaohui and Chen dynasty scholang of the science and engineering of Qingdao science and technology university in the fifth stage of Shanghai chemical industry, published the research on acrylamide modified melamine formaldehyde resin rigid foam, and studied the toughening effect of acrylamide on melamine formaldehyde resin rigid foam, wherein the appropriate addition amount of acrylamide monomer is 8-10%, and the use amount of initiator is 2.0 multiplied by 104～3.0×104mol/kg, and the mechanical property and the thermal stability of the rigid foam body made of the modified resin are tested and analyzed.
The Chinese invention patent ZL201310745020.7 discloses a method for toughening and modifying urea resin, which comprises the following steps: uniformly mixing a toughening agent acrylic polymer, a vinyl polymer or an acetal polymer with urea resin through dispersion equipment to obtain urea resin molding powder, wherein the toughening agent acrylic polymer, the vinyl polymer or the acetal polymer accounts for no more than 80% of the mass of the mixture; pressing 60-200 mesh urea-formaldehyde resin molding powder for 2-20 min at 80-200 ℃ and 5-60 MPa by using a flat vulcanizing machine to obtain an impact sample strip or a bending sample strip. The invention uses self-made toughener acrylic ester polymer, commercial acetal polymer or vinyl polymer to toughen and modify the urea-formaldehyde resin, wherein the best toughening effect is achieved by using the self-made acrylic ester polymer, the impact strength is 2.50kJ/m, and the bending strength is 85 MPa.
The Chinese patent application CN201710506435.7 discloses a starch emulsion modified urea-formaldehyde resin adhesive, which is prepared from the following raw materials in parts by weight: 10 parts of urea-formaldehyde resin, 1-10 parts of modified starch emulsion, 2-10 parts of polyvinyl acetate emulsion, 0.3-1 part of curing agent, 0.9-3 parts of reinforcing agent, 2-6 parts of water-based polymer, 0.03-0.1 part of modified auxiliary agent and 0.5-1.5 parts of filler. The adhesive provided by the invention can effectively reduce the formaldehyde release amount, has better environmental protection property, enhances the flexibility of the adhesive layer, improves the drying rate of the glue, shortens the curing time of the glue, reduces the moisture regain rate of the glue, reduces the production cost and improves the economic benefit.
The urea-formaldehyde resin has low price, sufficient raw materials and easy curing, and the cured resin has no toxicity, no color, good light resistance, hardness and scratch resistance, and the molecular structure contains polar oxygen atoms, so the adhesive force to the object surface is good; however, urea-formaldehyde resin also has certain defects, such as poor alkali resistance, high curing conditions, brittle cured product without toughness, large viscosity, high acid value and poor storage stability, and the storage life of some urea-formaldehyde resin adhesives is even only 15 days, thereby severely restricting the application of the urea-formaldehyde resin adhesives in other fields. The acrylate has good weather resistance, high transparency, good light and color retention, water and chemical resistance and the like, is quick to dry, convenient to construct and the like, but has relatively high price and insufficient hardness, and is difficult to meet the requirement of a high-hardness coating.
The above techniques show that the urea-formaldehyde resin modified acrylate has good mechanical properties, but the existing modification techniques for urea-formaldehyde resin have great limitations, can be only carried out by a macroscopic blending or mechanical blending method, and hardly reaches or exceeds the properties of stability, water resistance, alkali resistance, high toughness and the like of acrylate polymers in performance.
Disclosure of Invention
(1) Technical problem to be solved
Aiming at the defects of the prior art, the invention aims to provide a high-performance glass fiber coating and a preparation method thereof, and the glass fiber coating and the preparation method thereof aim to solve the technical problems of poor alkali resistance and poor storage stability of the conventional urea resin coating; by adopting the technical scheme, the water resistance, alkali resistance and storage stability of the coating can be effectively improved, and the coating has the performance advantages of urea-formaldehyde resin and acrylate resin and simultaneously improves the overall performance of the polymer.
(2) Technical scheme
In order to solve the technical problems, the invention provides a high-performance glass fiber coating, which is a urea-formaldehyde resin modified acrylate cationic emulsion and an interpenetrating network structure polymer thereof, and comprises the following raw materials in parts by mass: 40-70 parts of water, 20-30 parts of acrylate monomers, 1-5 parts of acrylate functional monomers, 10-30 parts of modified urea-formaldehyde resin glue, 0.5-5 parts of polymeric stabilizer, 0.1-1.5 parts of azo-bis-isobutyramidine hydrochloride, 0.1-0.5 part of azo-bis-isobutyronitrile, 0.1-3 parts of cationic emulsifier or cationic reaction type emulsifier, 4-7 parts of cationic starch dispersion, 0.05-0.5 part of acid-base buffer and 0.1-5 parts of chain transfer additive.
The urea resin modified acrylate cationic emulsion and the interpenetrating network structure polymer thereof are obtained by cation in-situ polymerization of the raw materials.
Preferably, the raw material components comprise, by mass: 50-60 parts of water, 25-30 parts of acrylate monomers, 2-5 parts of acrylate functional monomers, 15-25 parts of modified urea-formaldehyde resin glue, 1-4 parts of polymerization stabilizer, 0.1-1.5 parts of azo-bis-isobutyramidine hydrochloride, 0.1-0.3 part of azo-bis-isobutyronitrile, 0.1-3 parts of cationic emulsifier or cationic reaction type emulsifier, 4-7 parts of cationic starch dispersion liquid, 0.05-0.5 part of acid-base buffer and 0.1-5 parts of chain transfer assistant.
When the preferable raw material proportion is adopted, the water resistance and alkali resistance of the urea resin modified acrylate cationic emulsion obtained by in-situ cationic polymerization and the interpenetrating network structure polymer thereof can be improved within a certain range.
The acrylic ester monomer comprises vinyl monomers, and can be one or more of vinyl versatate such as acrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, isooctyl acrylate, tert-butyl methacrylate, vinyl acetate and the like.
Preferably, the acrylate functional monomer is one or more of acrylamide, diacetone acrylamide, N-methylolacrylamide, N- (isobutoxy) methacrylamide, glycidyl acrylate, glycidyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate.
Preferably, the cationic emulsifier or cationic reactive emulsifier is one or more of cetyl trimethyl ammonium bromide, dodecyl trimethyl ammonium bromide, methacryloxy trimethyl ammonium bromide, propenyl triethyl ammonium bromide, benzyl trimethyl ammonium tribromide, trimethyl vinyl ammonium bromide, vinyl trimethyl ammonium chloride, benzyl vinyl trimethyl ammonium chloride.
Preferably, the polymeric stabilizer is one or two of hexadecanol, hexadecane, hydrogenpolysiloxane, n-hexanol, isopropanol and polyvinyl alcohol.
Preferably, the chain transfer assistant is one or two of mercaptoethanol and dodecyl mercaptan.
Preferably, the cationic starch dispersion is prepared by adding isopropanol into cationic starch and gelatinizing at high temperature, and the mass concentration of the cationic starch is 20-30%.
Preferably, the preparation process of the modified urea-formaldehyde resin adhesive is as follows:
adding a first batch of formaldehyde into a reaction kettle, adjusting the pH value of the formaldehyde to 8.5-9, adding a first batch of urea into the reaction kettle, heating the mixture to 90 ℃ for reaction for 30 minutes, adjusting the pH value of the mixture to 4.5-5, adding acrylamide and a second batch of formaldehyde into the mixture after the reaction is completed (namely the viscosity of a reactant reaches a corresponding degree), adjusting the pH value to 8.5-9, after 10 minutes of reaction, adding melamine into the mixture, reacting for 20 minutes, adjusting the pH value to 7.5-8, adding water (a proper amount) after the reaction is completed (namely the viscosity of reactants reaches a corresponding degree), adjusting the pH value to 6.5-7, adding a second batch of urea, cooling to 80 ℃, adding azodiisobutyl amidine hydrochloride to react for 30 minutes, cooling, and ammonia water is used for neutralization, the pH value is adjusted to 7.5-8, and the modified urea-formaldehyde resin adhesive (namely the modified micro-crosslinked urea-formaldehyde resin) is obtained after discharging.
Further, in the preparation process of the modified urea-formaldehyde resin adhesive, the molar ratio of the total amount of formaldehyde, urea, melamine, acrylamide and azodiisobutylamine hydrochloride is preferably 2: 1.4:0.4:0.2: 0.002.
the invention is different from the traditional preparation of urea-formaldehyde resin, melamine and acrylamide are adopted to modify urea-formaldehyde resin, through the reaction of excessive formaldehyde with urea and the control of different pH values, hydroxymethyl urea and dimethylol urea can be selectively generated, meanwhile, under the alkaline condition, the methylol reaction of the acrylamide and the formaldehyde can prepare the hydroxymethyl acrylamide, and the reaction equation is as follows.
Under alkaline conditions, methylolation reaction of melamine and formaldehyde can prepare methylol melamine derivative, and the reaction equation is as shown in the following formula.
The methylol acrylamide is condensed with trimethylol melamine under neutral or weak alkaline condition, and is embedded into melamine formaldehyde resin as a flexible chain, and the reaction equation is as follows.
As above, the condensation polymerization reaction between the hydroxymethyl group on one triazine ring and the hydroxymethyl group on the other triazine ring firstly generates ether bond and further removes a molecule of formaldehyde to become methylene bond; the polycondensation reaction between triazine rings containing more methylol groups is slower, whereas the polycondensation reaction between triazine rings containing less methylol groups is faster because more active hydrogen atoms remain on the triazine rings. In addition, under acidic and heating conditions, methylol ureas can also react like a reaction, which is shown in the following formula.
The melamine plays a role in improving the crosslinking reaction and the rigidity of a crosslinking network of the glue layer, the introduction of unsaturated double bonds prepares for generating a micro-crosslinking structure, cationic polymerization is generated under a neutral condition, micro-crosslinking is generated, and part of unreacted acrylamide is subjected to self-polymerization in water after free radicals are introduced to produce polyacrylamide; under the conditions of acidity and 80 ℃, formaldehyde can also react with polyacrylamide similarly, and the reaction formula is shown as the following formula.
After the urea resin is used for modifying the acrylate and preparing the interpenetrating network structure polymer, methylene urea generated by dehydrating the monomethyl urea can be combined with polyacrylamide during later curing, and a condensation product is generated by reaction, wherein the reaction equation is as follows.
The modified urea-formaldehyde resin prepared by the method has good water solubility and polymerization stability, and meanwhile, the proper crosslinking degree of the modified urea-formaldehyde resin can restrain the acrylate monomer swelled in the modified urea-formaldehyde resin during cationic polymerization to prevent phase separation, thereby creating conditions for preparing the subsequent urea-formaldehyde resin modified acrylate interpenetrating network structure polymer; but in order to ensure the stability of emulsion particles and prevent the urea-formaldehyde resin from being separated out due to micelle nucleation of the emulsion particles, the technology of the invention adopts a nucleation mechanism initiated in submicron monomer droplets, dissolves an oil-soluble initiator in a monomer, and swells the monomer in urea-formaldehyde resin micro-and nano-particles together for polymerization and molding.
The technology for initiating nucleation in submicron monomer droplets is a new particle nucleation mechanism firstly proposed by Ugelstad et al in 1973, and the technology enables the monomer droplets to form stable submicron particles (50-500 nm) by introducing a small amount of emulsifier and co-emulsifier and combining with a fine emulsification dispersion technology, so that the specific surface area is greatly increased, a free emulsifier forms micelles or stable homogeneous nucleation in a water phase, the monomer droplets become a main nucleation site in the polymerization process, emulsion instability caused by diffusion can be effectively reduced, and the particle size and distribution of latex are easy to control.
The invention also provides a preparation method of the high-performance glass fiber coating, which is used for preparing the glass fiber coating, wherein the glass fiber coating is the urea-formaldehyde resin modified acrylate cationic emulsion and the interpenetrating network structure polymer thereof, and the preparation method comprises the following specific steps:
mixing an acrylate monomer and an acrylate functional monomer, dissolving azodiisobutyronitrile in the acrylate monomer and the acrylate functional monomer, adding the modified urea-formaldehyde resin adhesive into the acrylate monomer and the acrylate functional monomer, and shearing, dispersing and swelling for 0.5-1 hour in an ice bath; adding an acid-base buffer, a chain transfer auxiliary agent, a part of cationic emulsifier or cationic reactive emulsifier and cationic starch dispersion liquid in a formula amount into a part of water in a formula amount to prepare emulsified water; adding the swelled resin and monomer into emulsified water, and shearing and emulsifying to obtain a pre-emulsion (the particle size of the pre-emulsion is less than 1 μm);
adding the polymerization stabilizer and the cationic emulsifier or the cationic reactive emulsifier with the rest formula amount into the water with the rest formula amount to prepare a base solution;
step three, dropwise adding the pre-emulsion into the base solution, carrying out emulsion polymerization by adopting a starvation dropwise adding method, and heating to 60-90 ℃ for heat preservation after the pre-emulsion is completely dropwise added;
and step four, adding azodiisobutyl amidine hydrochloride into the mixed solution, preserving heat at 85-90 ℃, cooling and filtering, wherein the filtrate is the obtained glass fiber coating (which is an emulsion type high-performance glass fiber coating polymer, namely the modified urea-formaldehyde resin modified acrylate resin interpenetrating network cationic emulsion).
The key concept of the preparation method of the glass fiber coating is as follows: the technical scheme includes that modified urea-formaldehyde resin is used as a fixed phase, acrylate monomers are used for swelling, the swollen urea-formaldehyde resin is sheared and dispersed by a high-shear dispersion machine and is dispersed in a pre-emulsion of the acrylate monomers in a nanometer particle size, and an initiator dissolved in the monomers is used for promoting monomer droplets of the pre-emulsion of a mixture to initiate polymerization, so that the acrylate modified urea-formaldehyde resin LIPN structure water dispersion system is prepared by the method. The polymer can generate secondary crosslinking at high temperature after forming a film, so that a urea-formaldehyde resin system and an acrylate resin system respectively generate self-crosslinking reaction to generate a high-performance coating with an interpenetrating network structure.
The invention, through the swelling effect of acrylate to urea-formaldehyde resin and the high-efficient shear dispersion performance of a high-shear dispersion machine, disperses the modified urea-formaldehyde resin of fixed acrylate monomer in the pre-emulsion with nanometer granularity, polymerizes the monomer liquid drop in the fixed phase into nucleus by the submicron monomer liquid drop nucleation technology, and prepares the urea-formaldehyde resin modified acrylate cationic emulsion with the LIPN structure by the method. The system not only has the performance advantages of the urea-formaldehyde resin and the acrylate resin, but also improves the overall performance of the polymer, reduces the raw material cost of the acrylate, and simultaneously, the polymer is crosslinked under the heating condition after film formation, so that the urea-formaldehyde resin system and the acrylate resin system respectively generate self-crosslinking reaction to generate a high-performance coating layer with an interpenetrating network structure.
In addition, the cationic emulsion polymerization is used in the invention because the cationic polymerization can react in an environment with a high system pH value, and the polymerization environment is favorable for the stability of the urea-formaldehyde resin, so that the further crosslinking of the urea-formaldehyde resin can be effectively inhibited.
(3) Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
the technical scheme of the invention utilizes a particle nucleation mechanism, uses micro-crosslinked modified urea-formaldehyde resin as a carrier, uses an acrylate monomer for swelling, and forcibly emulsifies into pre-emulsion by utilizing the high-shear dispersing action of a high-shear emulsifying disperser with the help of an emulsifier and an auxiliary emulsifier; the polymer with the structure of urea-formaldehyde resin and acrylate resin LIPN can be respectively crosslinked under specific conditions after the polymer is formed into a film, so that an interpenetrating network structure polymer coating with strong water resistance, excellent alkali resistance and high storage stability is formed, and the water resistance and alkali resistance of the polymer can reach or exceed those of a pure acrylate emulsion when the dosage of the urea-formaldehyde resin is close to 50 percent; meanwhile, the obtained emulsion has the properties of environmental protection, stability and safety, has the effects of antibiosis and mildew prevention, has the characteristics of transparency, high hardness and high toughness, and can be widely used in the fields of printing adhesive cement, paint, adhesive, coating cement and the like.
According to the invention, the modified polymer achieves the required performance by utilizing scientific and reasonable raw material ratio, through acrylamide and melamine modified urea-formaldehyde resin and initiating cationic polymerization by azo-diisobutymidine hydrochloride to generate micro-crosslinking. Meanwhile, the invention utilizes the cation polymerization to take the swelled urea-formaldehyde resin as A, and prepares the self-crosslinked acrylic ester polymer B through the particle nucleation mechanism, so that the two polymers are doped with each other, and can be crosslinked in different modes after being dried to form a film, and finally the urea-formaldehyde resin modified acrylic ester interpenetrating network structure polymer is formed, so that the urea-formaldehyde resin modified acrylic ester interpenetrating network structure polymer has various characteristics of solvent resistance, water resistance, alkali resistance, high toughness and high strength, and has wide application and low price.
The modified micro-crosslinked urea-formaldehyde resin adhesive has the characteristics of moderate crosslinking density and good stability, is beneficial to in-situ polymerization of the acrylic ester monomer which is bound to swell during polymerization, and simultaneously ensures the stability of the acrylic ester monomer in a cationic polymerization process. Meanwhile, the invention perfects the process of initiating nucleation in the submicron monomer droplets by the effective synergistic cooperation of the polymerization process and the polymerization stabilizer, and prepares the stable emulsion particles.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the technical solutions in the prior art will be briefly described below, it is obvious that the drawings in the following description are only one embodiment of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a transmission electron microscope analysis chart of the urea resin modified acrylate cationic emulsion obtained in example 1.
FIG. 2 is a particle size analysis chart of the urea resin-modified acrylic cationic emulsion obtained in example 1.
Detailed Description
In order to make the technical means, the original characteristics, the achieved purposes and the effects of the invention easily understood and obvious, the technical solutions in the embodiments of the present invention are clearly and completely described below to further illustrate the invention, and obviously, the described embodiments are only a part of the embodiments of the present invention, but not all the embodiments.
1. The raw materials and sources used in the following examples are shown in table 1 below:
TABLE 1 raw materials and sources used
2. Preparation of modified micro-crosslinked urea-formaldehyde resin adhesive
(1) Raw material proportion of modified urea-formaldehyde resin adhesive
Wherein, formaldehyde: urea: melamine: acrylamide: the molar ratio of the total amount of azodiisobutyamidine hydrochloride used in each case was 2: 1.4:0.4:0.2: 0.002.
(2) the formulation of the modified urea-formaldehyde resin is shown in table 2 below:
TABLE 2 modified Urea-formaldehyde resin adhesive formulation
| Name of raw materials | Dosage (kilogram) |
| Formaldehyde (I) | 171.5 |
| Urea (1) | 67.2 |
| Urea (2) | 16.8 |
| Acrylamide | 14 |
| Melamine | 50.4 |
| Azo-bis-isobutyramidine hydrochloride | 0.45 |
| 20% sodium hydroxide | Proper amount of |
| 15% hydrogen chloride | Proper amount of |
| Water (W) | Proper amount of |
(3) Preparation process of modified urea-formaldehyde resin adhesive
Adding a first batch of formaldehyde into a reaction kettle, adjusting the pH value of the formaldehyde to 8.5-9, adding a first batch of urea into the reaction kettle, heating the mixture to 90 ℃ for reaction for 30 minutes, adjusting the pH value of the mixture to 4.5-5, observing that the viscosity of a reactant reaches a corresponding degree after the reaction is completed, adding acrylamide and a second batch of formaldehyde into the reaction kettle, adjusting the pH value of the reactant to 8.5-9, adding melamine into the reaction kettle for reaction for 20 minutes after the reaction is performed for 10 minutes, adjusting the pH value of the reaction kettle to 7.5-8, adding a proper amount of water after the reaction is completed, observing that the viscosity of the reactant reaches the corresponding degree, adjusting the pH value of the reaction kettle to 6.5-7, adding a second batch of urea, cooling the reaction kettle to 80 ℃ and adding azodiisobutyl amidine hydrochloride for reaction for 30 minutes, cooling the reaction kettle, neutralizing the reaction kettle with ammonia water, adjusting the pH value of the reaction kettle to 7.5-8, discharging the modified urea-formaldehyde resin glue, the modified micro-crosslinked urea-formaldehyde resin is a milky and slightly thick liquid with the solid content of more than 40 percent.
Example 1
A preparation method of urea resin modified acrylate cationic emulsion and interpenetrating network structure polymer thereof comprises the following steps (the following mixture ratio is parts by weight, unit is kilogram):
1) preparation of cationic seed emulsion
The seed emulsion comprises the following components in percentage by weight: cationic starch gum (25%) 7.4, CTAB 0.95, AIBA 0.3, water 160, St 7.2, BA 5.4, HEA 2.0.
Adding bottoming water into a reaction kettle, adding a dispersing agent (cationic starch dispersion liquid with the mass concentration of 25%), an emulsifier (cationic emulsifier or cationic reaction type emulsifier) and azodiisobutylamine hydrochloride while stirring, introducing nitrogen to remove oxygen and heating after vacuum degassing, dropwise adding a bottoming monomer at 70 ℃, keeping the temperature for 30min after completing dripping, and finishing the preparation of the bottoming seed emulsion.
2) Preparation of the Pre-emulsion
The proportion of the emulsification (water phase) of the pre-emulsion is as follows: CTAB 5, dispersant (25%) 14.8, water 80, cetyl alcohol 2.
The proportion of the pre-emulsion monomer swelling modified urea-formaldehyde resin (oil phase) is as follows: st 45, MMA 20, BA 48.6, GMA 2, AA 1.5, N-MA 2.5, modified urea-formaldehyde resin (40%) 100, PHMS 1.2, AIBN 0.6.
Preparing a pre-emulsion while priming: firstly, dissolving an emulsifier, a stabilizer, a dispersant and an initiator in hot water at 55 ℃ according to the proportion of a pre-emulsion emulsified water phase for later use, then dissolving the oil-soluble initiator in butyl acrylate according to the proportion of a pre-emulsion monomer swelling modified urea-formaldehyde resin phase, and then adding other monomers and adding the monomers into 40% modified urea-formaldehyde resin for shear swelling; the swelling process needs a high-shear dispersion emulsifying machine under a high-shear condition, an ice water bath is used for preventing mechanical heat enrichment during shearing, the shearing time is 1 hour, an emulsified water phase is added for emulsification after complete shearing swelling, and the emulsification time is 5 minutes to form stable emulsion.
3) And dropwise addition of the preemulsion
And after the seed emulsion polymerization is finished, synchronously dropwise adding the pre-emulsion for 3-5 hours at the temperature of 70-75 ℃, heating to 80 ℃ after the pre-emulsion is completely dropwise added, preserving heat for 30min, then heating to 85 ℃, preserving heat for 1 hour, and cooling.
4) And the results obtained
After the emulsion is cooled, filtering the mixture by a 120-mesh sieve to obtain a liquid phase, adding a proper amount of antifoaming agent and flatting agent, and finally packaging and warehousing; the appearance was visually observed and the shelf life was observed, and the results are shown in the following Table 3.
The emulsion was coated at 160g/m2The building strength reinforced glass fiber mesh cloth is coated with glue with the amount of 13-15g/m2The drying condition is drying at 150 ℃ for 90 seconds. And testing the tensile breaking strength according to GB/T7689.5-2013, and testing the alkali-resistant retention rate according to GB/T20101-2006, wherein the specific test results are shown in the following table 4.
Example 2
A preparation method of urea resin modified acrylate cationic emulsion and interpenetrating network structure polymer thereof comprises the following steps (the following mixture ratio is parts by weight, unit is kilogram):
1) preparation of cationic seed emulsion
The seed emulsion comprises the following components in percentage by weight: cationic starch gum (25%) 7.4, CTAB 0.95, AIBA 0.3, water 160, BA 12.6, HPA 2.0.
Adding bottoming water into a reaction kettle, adding a dispersing agent (cationic starch dispersion liquid with the mass concentration of 25%), an emulsifier (cationic emulsifier or cationic reaction type emulsifier) and azodiisobutylamine hydrochloride while stirring, introducing nitrogen to remove oxygen and heating after vacuum degassing, dropwise adding a bottoming monomer at 70 ℃, keeping the temperature for 30min after completing dripping, and finishing the preparation of the bottoming seed emulsion.
2) Preparation of the Pre-emulsion
The proportion of the emulsification (water phase) of the pre-emulsion is as follows: DMC 15, water 60, cetyl alcohol 2.
The proportion of the pre-emulsion monomer swelling modified urea-formaldehyde resin (oil phase) is as follows: EA 80, MMA 6, BA 28, HEMA 2, AA 1.5, IBMA 2.5, modified urea-formaldehyde resin (40%) 180, PHMS 1.2, AIBN 0.6.
Preparing a pre-emulsion while priming: firstly, dissolving an emulsifier, a stabilizer, a dispersant and an initiator in hot water at 55 ℃ according to the proportion of a pre-emulsion emulsified water phase for later use, then dissolving the oil-soluble initiator in butyl acrylate according to the proportion of a pre-emulsion monomer swelling modified urea-formaldehyde resin phase, and then adding other monomers and adding the monomers into 40% modified urea-formaldehyde resin for shear swelling; the swelling process needs a high-shear dispersion emulsifying machine under a high-shear condition, an ice water bath is used for preventing mechanical heat enrichment during shearing, the shearing time is 1 hour, an emulsified water phase is added for emulsification after complete shearing swelling, and the emulsification time is 5 minutes to form stable emulsion.
3) And dropwise addition of the preemulsion
And after the seed emulsion polymerization is finished, synchronously dropwise adding the pre-emulsion for 3-5 hours at the temperature of 70-75 ℃, heating to 80 ℃ after the pre-emulsion is completely dropwise added, preserving heat for 30min, then heating to 85 ℃, preserving heat for 1 hour, and cooling.
4) And the results obtained
After the emulsion is cooled, filtering the mixture by a 120-mesh sieve to obtain a liquid phase, adding a proper amount of antifoaming agent and flatting agent, and finally packaging and warehousing; the appearance was visually observed and the shelf life was observed, and the results are shown in the following Table 3.
The emulsion was coated at 160g/m2The building strength reinforced glass fiber mesh cloth is coated with glue with the amount of 13-15g/m2The drying condition is drying at 150 ℃ for 90 seconds. And testing the tensile breaking strength according to GB/T7689.5-2013, and testing the alkali-resistant retention rate according to GB/T20101-2006, wherein the specific test results are shown in the following table 4.
Example 3
A preparation method of urea resin modified acrylate cationic emulsion and interpenetrating network structure polymer thereof comprises the following steps (the following mixture ratio is parts by weight, unit is kilogram):
1) preparation of cationic seed emulsion
The seed emulsion comprises the following components in percentage by weight: cationic starch gum (25%) 7.4, CTAB 0.95, AIBA 0.3, water 160, BA 12.6, DPA 2.0.
Adding bottoming water into a reaction kettle, adding a dispersing agent (cationic starch dispersion liquid with the mass concentration of 25%), an emulsifier (cationic emulsifier or cationic reaction type emulsifier) and azodiisobutylamine hydrochloride while stirring, introducing nitrogen to remove oxygen and heating after vacuum degassing, dropwise adding a bottoming monomer at 70 ℃, keeping the temperature for 30min after completing dripping, and finishing the preparation of the bottoming seed emulsion.
2) Preparation of the Pre-emulsion
The proportion of the emulsification (water phase) of the pre-emulsion is as follows: CTAB 5, dispersant (25%) 14.8, water 80, cetyl alcohol 2.
The proportion of the pre-emulsion monomer swelling modified urea-formaldehyde resin (oil phase) is as follows: ST 45, MMA 20, BA 48.6, DAAM 3, MAA 1.5, NHEMAA 2.5, modified urea-formaldehyde resin (40%) 60, n-butanol 1.2, AIBN 0.8.
Preparing a pre-emulsion while priming: firstly, dissolving an emulsifier, a stabilizer, a dispersant and an initiator in hot water at 55 ℃ according to the proportion of a pre-emulsion emulsified water phase for later use, then dissolving the oil-soluble initiator in butyl acrylate according to the proportion of a pre-emulsion monomer swelling modified urea-formaldehyde resin phase, and then adding other monomers and adding the monomers into 40% modified urea-formaldehyde resin for shear swelling; the swelling process needs a high-shear dispersion emulsifying machine under a high-shear condition, an ice water bath is used for preventing mechanical heat enrichment during shearing, the shearing time is 1 hour, an emulsified water phase is added for emulsification after complete shearing swelling, and the emulsification time is 5 minutes to form stable emulsion.
3) And dropwise addition of the preemulsion
And after the seed emulsion polymerization is finished, synchronously dropwise adding the pre-emulsion for 3-5 hours at the temperature of 70-75 ℃, heating to 80 ℃ after the pre-emulsion is completely dropwise added, preserving heat for 30min, then heating to 85 ℃, preserving heat for 1 hour, and cooling.
4) And the results obtained
After the emulsion is cooled, filtering the mixture by a 120-mesh sieve to obtain a liquid phase, adding a proper amount of antifoaming agent and flatting agent, and finally packaging and warehousing; the appearance was visually observed and the shelf life was observed, and the results are shown in the following Table 3.
The emulsion was coated at 160g/m2The building strength reinforced glass fiber mesh cloth is coated with glue with the amount of 13-15g/m2The drying condition is drying at 150 ℃ for 90 seconds. And testing the tensile breaking strength according to GB/T7689.5-2013, and testing the alkali-resistant retention rate according to GB/T20101-2006, wherein the specific test results are shown in the following table 4.
Example 4
A preparation method of urea resin modified acrylate cationic emulsion and interpenetrating network structure polymer thereof comprises the following steps (the following mixture ratio is parts by weight, unit is kilogram):
1) preparation of cationic seed emulsion
The seed emulsion comprises the following components in percentage by weight: polyvinyl alcohol 1799 of 8, CTAB of 0.95, AIBA of 0.3, water of 160, BA of 12.6, DPA of 2.0.
Adding bottoming water into a reaction kettle, adding a dispersing agent (cationic starch dispersion liquid with the mass concentration of 25%), an emulsifier (cationic emulsifier or cationic reaction type emulsifier) and azodiisobutylamine hydrochloride while stirring, introducing nitrogen to remove oxygen and heating after vacuum degassing, dropwise adding a bottoming monomer at 70 ℃, keeping the temperature for 30min after completing dripping, and finishing the preparation of the bottoming seed emulsion.
2) Preparation of the Pre-emulsion
The proportion of the emulsification (water phase) of the pre-emulsion is as follows: DMC 15 and water 80.
The proportion of the pre-emulsion monomer swelling modified urea-formaldehyde resin (oil phase) is as follows: VAc 45, MMA 30, BA 40, NMA 3, AA 1.5, NHEMAA 2.5, modified urea-formaldehyde resin (40%) 120, n-butanol 1.5, AIBN 0.8.
Preparing a pre-emulsion while priming: firstly, dissolving an emulsifier, a stabilizer, a dispersant and an initiator in hot water at 55 ℃ according to the proportion of a pre-emulsion emulsified water phase for later use, then dissolving the oil-soluble initiator in butyl acrylate according to the proportion of a pre-emulsion monomer swelling modified urea-formaldehyde resin phase, and then adding other monomers and adding the monomers into 40% modified urea-formaldehyde resin for shear swelling; the swelling process needs a high-shear dispersion emulsifying machine under a high-shear condition, an ice water bath is used for preventing mechanical heat enrichment during shearing, the shearing time is 1 hour, an emulsified water phase is added for emulsification after complete shearing swelling, and the emulsification time is 5 minutes to form stable emulsion.
3) And dropwise addition of the preemulsion
And after the seed emulsion polymerization is finished, synchronously dropwise adding the pre-emulsion for 3-5 hours at the temperature of 70-75 ℃, heating to 80 ℃ after the pre-emulsion is completely dropwise added, preserving heat for 30min, then heating to 85 ℃, preserving heat for 1 hour, and cooling.
4) And the results obtained
After the emulsion is cooled, filtering the mixture by a 120-mesh sieve to obtain a liquid phase, adding a proper amount of antifoaming agent and flatting agent, and finally packaging and warehousing; the appearance was visually observed and the shelf life was observed, and the results are shown in the following Table 3.
The emulsion was coated at 160g/m2The building strength reinforced glass fiber mesh cloth is coated with glue with the amount of 13-15g/m2The drying condition is drying at 150 ℃ for 90 seconds. And testing the tensile strength according to GB/T7689.5-2013The tensile fracture strength is tested according to GB/T20101-2006 alkali-resistant retention rate, and specific test results are shown in the following table 4.
Comparative example 1
The preparation method comprises the following steps of (by weight, in units of kilograms):
1) preparation of cationic seed emulsion
The seed emulsion comprises the following components in percentage by weight: cationic starch gum (25%) 7.4, CTAB 0.95, AIBA 0.3, water 160, BA 12.6, HPA 2.0.
Adding bottoming water into a reaction kettle, adding a dispersing agent (cationic starch dispersion liquid with the mass concentration of 25%), an emulsifier (cationic emulsifier or cationic reaction type emulsifier) and azodiisobutylamine hydrochloride while stirring, introducing nitrogen to remove oxygen and heating after vacuum degassing, dropwise adding a bottoming monomer at 70 ℃, keeping the temperature for 30min after completing dripping, and finishing the preparation of the bottoming seed emulsion.
2) Preparation of the Pre-emulsion
The proportion of the emulsification (water phase) of the pre-emulsion is as follows: DMC 15, water 60, cetyl alcohol 2.
The proportion of the pre-emulsion monomer swelling modified urea-formaldehyde resin (oil phase) is as follows: EA 80, MMA 6, BA 28, HEMA 2, AA 1.5, IBMA 2.5, PHMS 1.2, AIBN 0.6.
Specifically, no modified urea-formaldehyde resin was added in the preparation of the comparative example pre-emulsion.
Preparing a pre-emulsion while priming: firstly, dissolving an emulsifier, a stabilizer, a dispersant and an initiator in hot water at 55 ℃ according to the proportion of a pre-emulsion emulsified water phase for later use, then dissolving the oil-soluble initiator in butyl acrylate according to the proportion of a pre-emulsion monomer swelling modified urea-formaldehyde resin phase, and then adding other monomers and adding the monomers into 40% modified urea-formaldehyde resin for shear swelling; the swelling process needs a high-shear dispersion emulsifying machine under a high-shear condition, an ice water bath is used for preventing mechanical heat enrichment during shearing, the shearing time is 1 hour, an emulsified water phase is added for emulsification after complete shearing swelling, and the emulsification time is 5 minutes to form stable emulsion.
3) And dropwise addition of the preemulsion
And after the seed emulsion polymerization is finished, synchronously dropwise adding the pre-emulsion for 3-5 hours at the temperature of 70-75 ℃, heating to 80 ℃ after the pre-emulsion is completely dropwise added, preserving heat for 30min, then heating to 85 ℃, preserving heat for 1 hour, and cooling.
4) And the results obtained
After the emulsion is cooled, filtering the mixture by a 120-mesh sieve to obtain a liquid phase, adding a proper amount of antifoaming agent and flatting agent, and finally packaging and warehousing; the appearance was visually observed and the shelf life was observed, and the results are shown in the following Table 3.
And then adding 180 parts of modified urea-formaldehyde resin into the obtained emulsion in a manner that the emulsion is slowly dripped with the modified urea-formaldehyde resin glue during stirring for 30 minutes, and filtering by 120 meshes after dripping to obtain a liquid phase. The appearance was visually observed and the shelf life was observed, and the results are shown in the following Table 3.
Comparative example 2
This comparative example was conducted exactly as in example 1, but with the stabilizer removed from the formulation.
Test results
1. The specific results of the appearance and storage stability tests are shown in table 3 below:
TABLE 3 product appearance and storage stability
| Product type | Appearance of the product | Storage stability (Tian) |
| Example 1 | Milky white, slight blue light | ﹥90 |
| Example 2 | Is in a milk-white state, | ﹥90 |
| example 3 | Milk white | ﹥90 |
| Example 4 | Milky white, thick emulsion | ﹥30 |
| Comparative example 1 | White and blue | ﹥15 |
| Comparative example 2 | A large amount of solid small particles are separated out |
2. Emulsion coated glass fiber mesh fabric performance test
The tensile breaking strength is tested according to GB/T7689.5-2013, the alkali-resistant retention rate is tested according to GB/T20101-2006, and the specific test results of each embodiment are shown in the following table 4:
TABLE 4 Performance test results for emulsion coated fiberglass mesh products
3. Emulsion latex particle projection electron microscope analysis
The urea resin modified acrylate cationic emulsion obtained in example 1 is subjected to a Transmission Electron Microscope (TEM) analysis to obtain a transmission electron microscope analysis image, a 120kv Transmission Electron Microscope (TEM) instrument of hitachi, japan is adopted, 1 drop of the emulsion obtained in example 1 is placed into a conical flask, 50ml of phosphotungstic acid aqueous solution (mass percentage concentration is 1%) is added for dyeing, the mixture is vibrated for five minutes under ultrasound, the mixture is stood for 40 minutes, a little of the mixture is dropped on a copper net, and after drying, the appearance of the mixture is observed under the TEM.
The transmission electron microscope shows that the urea resin modified acrylic acid cation latex particles are regular spheres, the particle size distribution is wide, the particle size distribution is between 150nm and 300nm, a core-shell structure can be seen, and common polymers with the LIPN structure all have the core-shell structure.
4. Particle size analysis of latex particles
The urea resin modified acrylate cationic emulsion obtained in example 1 was subjected to particle size analysis to obtain a particle size analysis chart, and the emulsion obtained in example 1 was analyzed by a Zetasizer Nano-ZS nanometer particle size and Zeta potential analyzer of Malvern, UK, wherein the average particle size was 252.2nm, the latex particles were in monomodal distribution, and the particle size was in accordance with the technique of nucleation of submicron monomer droplets, i.e., stable submicron particles (50-500 nm) were formed from the monomer droplets.
Having thus described the principal technical features and basic principles of the invention, and the advantages associated therewith, it will be apparent to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, but is capable of other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description is described in terms of various embodiments, not every embodiment includes only a single embodiment, and such descriptions are provided for clarity only, and those skilled in the art will recognize that the embodiments described herein can be combined as a whole to form other embodiments as would be understood by those skilled in the art.
Claims (7)
1. The glass fiber coating is characterized by comprising the following raw materials in parts by mass: 40-70 parts of water, 20-30 parts of acrylate monomers, 1-5 parts of acrylate functional monomers, 10-30 parts of modified urea-formaldehyde resin glue, 0.5-5 parts of polymeric stabilizer, 0.1-1.5 parts of azo-bis-isobutyramidine hydrochloride, 0.1-0.5 part of azo-bis-isobutyronitrile, 0.1-3 parts of cationic emulsifier or cationic reaction type emulsifier, 4-7 parts of cationic starch dispersion liquid, 0.05-0.5 part of acid-base buffer and 0.1-5 parts of chain transfer additive;
the cationic starch dispersion liquid is prepared by adding isopropanol into cationic starch and pasting at high temperature, and the mass concentration of the cationic starch is 20-30%;
the preparation process of the modified urea-formaldehyde resin adhesive comprises the following steps: adding a first batch of formaldehyde into a reaction kettle, adjusting the pH value of the first batch of formaldehyde to 8.5-9, adding a first batch of urea into the reaction kettle, heating to 90 ℃ and reacting for 30 minutes, adjusting the pH value of the reaction kettle to 4.5-5, after the reaction is completed, adding acrylamide and a second batch of formaldehyde into the reaction kettle, adjusting the pH value of the reaction kettle to 8.5-9, after the reaction is performed for 10 minutes, adding melamine into the reaction kettle and reacting for 20 minutes, adjusting the pH value of the reaction kettle to 7.5-8, adding water into the reaction kettle after the reaction is completed, adjusting the pH value of the reaction kettle to 6.5-7, adding a second batch of urea, cooling to 80 ℃, adding azodiisobutyramidine hydrochloride into the reaction kettle and reacting for 30 minutes, cooling, neutralizing the reaction kettle with ammonia water, adjusting the pH value of the reaction kettle to 7.5-8, and discharging to obtain a modified urea-formaldehyde resin adhesive;
in the preparation process of the modified urea-formaldehyde resin adhesive, the molar ratio of the total amount of formaldehyde, urea, melamine, acrylamide and azodiisobutyl amidine hydrochloride is 2: 1.4:0.4:0.2: 0.002.
2. the glass fiber coating of claim 1, wherein the glass fiber coating comprises the following raw materials in parts by weight: 50-60 parts of water, 25-30 parts of acrylate monomers, 2-5 parts of acrylate functional monomers, 15-25 parts of modified urea-formaldehyde resin glue, 1-4 parts of polymerization stabilizer, 0.1-1.5 parts of azo-bis-isobutyramidine hydrochloride, 0.1-0.3 part of azo-bis-isobutyronitrile, 0.1-3 parts of cationic emulsifier or cationic reaction type emulsifier, 4-7 parts of cationic starch dispersion liquid, 0.05-0.5 part of acid-base buffer and 0.1-5 parts of chain transfer assistant.
3. The glass fiber coating of any one of claims 1 or 2, wherein the acrylate functional monomer is one or more of acrylamide, diacetone acrylamide, N-methylolacrylamide, N- (isobutoxy) methacrylamide, glycidyl acrylate, glycidyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate.
4. A glass fiber coating according to any of claims 1 or 2, wherein the cationic or cationic reactive emulsifier is one or more of cetyltrimethylammonium bromide, dodecyltrimethylammonium bromide, methacryloxytrimethylammonium bromide, propenyl triethylammonium bromide, benzyltrimethylammoniumbromide, trimethylammoniumbromide, vinyltrimethylammonium chloride, benzylvinyltrimethylammonium chloride.
5. A glass fibre coating as claimed in any one of claims 1 or 2, wherein the polymeric stabiliser is one or both of cetyl alcohol, hexadecane, a hydrogenpolysiloxane, n-hexyl alcohol, isopropyl alcohol, polyvinyl alcohol.
6. A glass fibre coating according to any of claims 1 or 2, wherein the chain transfer aid is one or both of mercaptoethanol and dodecyl mercaptan.
7. A method for preparing a glass fiber coating, which is used for preparing the glass fiber coating as claimed in any one of claims 1 to 6, and comprises the following specific steps:
mixing an acrylate monomer and an acrylate functional monomer, dissolving azodiisobutyronitrile in the acrylate monomer and the acrylate functional monomer, adding the modified urea-formaldehyde resin adhesive into the acrylate monomer and the acrylate functional monomer, and shearing, dispersing and swelling for 0.5-1 hour in an ice bath; adding an acid-base buffer, a chain transfer auxiliary agent, a part of cationic emulsifier or cationic reactive emulsifier and cationic starch dispersion liquid in a formula amount into a part of water in a formula amount to prepare emulsified water; adding the swelled resin and monomer into emulsified water, and performing shearing emulsification to prepare a pre-emulsion;
adding the polymerization stabilizer and the cationic emulsifier or the cationic reactive emulsifier with the rest formula amount into the water with the rest formula amount to prepare a base solution;
step three, dropwise adding the pre-emulsion into the base solution, carrying out emulsion polymerization by adopting a starvation dropwise adding method, and heating to 60-90 ℃ for heat preservation after the pre-emulsion is completely dropwise added;
and step four, adding azodiisobutyl amidine hydrochloride into the mixed solution, preserving heat at 85-90 ℃, and finally cooling and filtering to obtain filtrate, namely the obtained glass fiber coating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910153795.2A CN109912234B (en) | 2019-03-01 | 2019-03-01 | Glass fiber coating and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910153795.2A CN109912234B (en) | 2019-03-01 | 2019-03-01 | Glass fiber coating and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109912234A CN109912234A (en) | 2019-06-21 |
| CN109912234B true CN109912234B (en) | 2021-09-28 |
Family
ID=66962907
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910153795.2A Active CN109912234B (en) | 2019-03-01 | 2019-03-01 | Glass fiber coating and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109912234B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114045702B (en) * | 2021-11-18 | 2023-05-26 | 广东科力德新材料有限公司 | Polymer emulsion capable of recycling and degrading PE (polyethylene) paper laminated film |
| CN115477481A (en) * | 2022-09-14 | 2022-12-16 | 重庆海科保温材料有限公司 | Mineral oil for glass wool products and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101550218A (en) * | 2009-04-03 | 2009-10-07 | 江苏工业学院 | Polymer emulsion, preparation method and re-dispersible latex powder |
| CN105950082A (en) * | 2016-04-01 | 2016-09-21 | 合肥第六元素光电科技有限公司 | Colored pressure-sensitive adhesive, manufacturing method thereof, and manufactured pressure-sensitive adhesive tape |
| CN106519106A (en) * | 2016-10-18 | 2017-03-22 | 无锡海特新材料研究院有限公司 | Super-transparent acrylate pressure-sensitive adhesive emulsion capable of being coated at high speed as well as preparation method and application thereof |
| WO2017104671A1 (en) * | 2015-12-18 | 2017-06-22 | ジャパンコーティングレジン株式会社 | Method for producing aqueous synthetic resin emulsion, method for producing reemulsifiable synthetic resin powder, method for producing polymer cement mortar, aqueous synthetic resin emulsion, and reemulsifiable synthetic resin powder |
| CN107722205A (en) * | 2017-10-20 | 2018-02-23 | 任会平 | A kind of preparation method of weatherability Lauxite |
| CN108546313A (en) * | 2018-04-25 | 2018-09-18 | 江苏锐康新材料科技有限公司 | A kind of Halogen highly effective flame-retardant cation emulsion and preparation method thereof that nano material in-situ is modified |
-
2019
- 2019-03-01 CN CN201910153795.2A patent/CN109912234B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101550218A (en) * | 2009-04-03 | 2009-10-07 | 江苏工业学院 | Polymer emulsion, preparation method and re-dispersible latex powder |
| WO2017104671A1 (en) * | 2015-12-18 | 2017-06-22 | ジャパンコーティングレジン株式会社 | Method for producing aqueous synthetic resin emulsion, method for producing reemulsifiable synthetic resin powder, method for producing polymer cement mortar, aqueous synthetic resin emulsion, and reemulsifiable synthetic resin powder |
| CN105950082A (en) * | 2016-04-01 | 2016-09-21 | 合肥第六元素光电科技有限公司 | Colored pressure-sensitive adhesive, manufacturing method thereof, and manufactured pressure-sensitive adhesive tape |
| CN106519106A (en) * | 2016-10-18 | 2017-03-22 | 无锡海特新材料研究院有限公司 | Super-transparent acrylate pressure-sensitive adhesive emulsion capable of being coated at high speed as well as preparation method and application thereof |
| CN107722205A (en) * | 2017-10-20 | 2018-02-23 | 任会平 | A kind of preparation method of weatherability Lauxite |
| CN108546313A (en) * | 2018-04-25 | 2018-09-18 | 江苏锐康新材料科技有限公司 | A kind of Halogen highly effective flame-retardant cation emulsion and preparation method thereof that nano material in-situ is modified |
Non-Patent Citations (2)
| Title |
|---|
| 丙烯酰胺改性三聚氰胺甲醛树脂硬质泡沫体的研究;赵辉等;《上海化工》;20150515;第40卷(第5期);第12页 * |
| 改性脲醛树脂堵剂的制备研究;王小泉等;《西安石油学院学报》;20030926;第18卷(第5期);第61-63页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109912234A (en) | 2019-06-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DK168668B1 (en) | Aqueous polymer emulsion containing interlaced networks, method of making them and using them | |
| CN103045113B (en) | Preparation method of self-crosslinking IPN (interpenetrating network) organosilicone-acrylate copolymer emulsion pressure-sensitive adhesive | |
| CN101704981B (en) | Cationic polyacrylate emulsion and preparation method thereof | |
| CN101270225B (en) | Method for preparing binary dispersion composite emulsion of polyurethane acrylic acid | |
| CN109054570B (en) | Environment-friendly high-strength elastic coating and preparation method thereof | |
| CA1338364C (en) | Dispersion polymers based on ethylenically unsaturated monomers and containing urethane groups, process for their preparation, and their use | |
| CN103333352B (en) | A kind of preparation method of cross-linked graft modified polyvinyl alcohol surface reinforcing agent | |
| CA1337729C (en) | Process for the production of aqueous polymer dispersions, the dispersions obtainable by this process and their use for the production of coatings | |
| CN109912234B (en) | Glass fiber coating and preparation method thereof | |
| CN102372885A (en) | High viscosity polyvinyl acetate emulsion and preparation method thereof | |
| US9023919B2 (en) | Aqueous binder composition | |
| JP5254209B2 (en) | Use of aqueous polymer compositions as binders for fibrous or granular substrates | |
| EP2814885A1 (en) | Aqueous binder composition | |
| CN102399344B (en) | Self-thickening pure acrylic latex used in art paints, and preparation method thereof | |
| CN109942742B (en) | Water-dispersible glass fiber coating polymer and preparation method thereof | |
| CN109666366B (en) | Urea-formaldehyde resin waste material regenerated modified acrylate interpenetrating network structure polymer emulsion and preparation and curing method thereof | |
| EP3623391B1 (en) | Polymodal polymer compositions for coating applications | |
| CN111978474B (en) | Preparation method of low-viscosity high-hydroxyl-value polymer surface reinforcing agent for paper | |
| CN109439142B (en) | Acrylate modified nano powder coating interpenetrating network aqueous dispersion, preparation method and curing method thereof | |
| CN110183593B (en) | Core-shell type surface sizing reinforcing agent and preparation method thereof | |
| CN113249063B (en) | Water-based plastic substitute and preparation method thereof | |
| CN114671973B (en) | Water-based acrylic resin and preparation method and application thereof | |
| DE102011005638A1 (en) | Producing a molded body, comprises producing an aqueous dispersion of a polymer A, applying aqueous polymer dispersion A to granular and/or fibrous substrate, and carrying out thermal treatment of treated granular and/or fibrous substrate | |
| JPH03103404A (en) | Aqueous resin composition | |
| US10266662B2 (en) | Production of shaped articles |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230113 Address after: 332900 South of Gangxing Road and west of Binjianghe Road, Chengxigang District, Jiujiang Economic and Technological Development Zone, Jiujiang City, Jiangxi Province Patentee after: Jiujiang Huayuan New Material Co.,Ltd. Address before: 341410 West District of Longling Industrial Park, Nankang District, Ganzhou City, Jiangxi Province Patentee before: JIANGXI GANFENG GLASS FIBER NET Co.,Ltd. |